JPH0349873Y2 - - Google Patents

Description

[Detailed explanation of the idea]

[Industrial Field of Application] The present invention relates to a laminated composite material that can be processed by high-frequency welding, in which a polyolefin resin foam and a sheet or film made of a polymer resin other than the above-mentioned polyolefin resin are integrated by thermal bonding. be. [Prior art] Conventionally, polyolefin resin foam itself has thermal adhesive properties, but when it is actually bonded to a base material, skin material, etc., the bonding surface is treated with a primer, etc. Usually, methods of applying an adhesive treatment or interposing a heat-fusible film for heat-sealing are employed. However, processing that requires the application of adhesive, such as primer processing,
The process of applying the adhesive itself is complicated, and there is a problem in that the adhesive surface tends to blister due to residual solvent or air when using solvent-based adhesives or film adhesives. . When the heating temperature is raised to prevent this blistering, there is a problem that the foam side becomes stale and the performance and quality of the product deteriorates. Furthermore, it has been difficult to perform high-frequency welding on such laminated composite materials because the foam layer is easily crushed by high-frequency welding. [Purpose of the invention] The purpose of the invention is to prevent blistering on the adhesive surface between a polyolefin resin foam and a sheet or film made of a polymer resin other than the polyolefin resin, and to prevent the foam from becoming stale due to the prevention of this blistering. An object of the present invention is to provide a vehicle interior material that can be subjected to high-frequency welding processing and eliminates the above problems. [Structure of the invention] The object of the invention is as follows: At least one of a polyolefin resin foam and a sheet or film made of a polymer resin other than the polyolefin resin contains a petroleum resin,
This can be achieved by thermally bonding the polyolefin resin foam to a polymer resin sheet or film. 1 and 2 are schematic cross-sectional views showing one example of the laminated composite material of the present invention, respectively, in which 1 is a polyolefin resin foam layer, 2 is a polymer resin sheet layer, and 3 is a skin material layer. be. The polyolefin resin constituting the foam of the present invention includes various known polyolefins, such as polyethylene resins obtained by polymerization methods such as high-pressure method, medium-pressure method, and low-pressure method, ethylene and α-olefin, vinyl acetate, Examples include copolymer resins with acrylic acid and the like, and propylene copolymers copolymerized with 1 to 15% by weight of α-olefin in random, block, or random block shapes. Further, the resin composition may be a mixture of resins having compatibility with these resins as appropriate within a range that can achieve the object of the present invention. The polymer resin sheet or film may include polyolefins other than the polyolefin resins constituting the foam, such as polyethylene, polypropylene, and copolymers thereof, and acrylonitrile-butadiene-styrene copolymer resins (so-called
There are sheets and films (with a thickness of about 5 mm to 0.02 mm) made of ABS resin, etc., and low-foam sheets with a foaming ratio of about 3 times or less. Inorganic additives such as materials, ultraviolet absorbers, stabilizers, and colorants may be blended, and patterns such as pictures may be formed by printing or the like. A feature of the present invention is that at least one of the polyolefin resin foam and the polymer resin sheet or film contains petroleum resin, and by blending the petroleum resin, the two can be laminated and thermally bonded. Therefore, it is integrated, that is, made into a composite material. Natural and synthetic petroleum resins used in this invention include polymerizable substances obtained by naphtha cracking, such as hydrogenated hydrocarbon resins, rosin resins, terpene resins, and chroman resins, such as olefins, diolefins, and alkenyl aromatic resins. There are olefinic petroleum resins and aromatic petroleum resins obtained by polymerizing polyesters and the like. Such petroleum resins may or may not contain polar groups, but resins without polar groups are preferred. Here, petroleum resins having no polar groups include hydroxyl groups (-OH), carboxyl groups (-COOH), halogen groups (-X), sulfone groups (-SO ₃ Y, Y is H,
It does not have polar groups such as Na, 1/2Mg, etc. and their modified products. That is, it is a resin whose main raw material is a cyclopentadiene-based or higher olefin-based hydrocarbon that is directly derived from a petroleum-based unsaturated hydrocarbon. For example, the expression An example of this is a hydrogenated alicyclic petroleum resin ("ESCOLETS" manufactured by Etsuo Kagaku Co., Ltd.) whose main component is the component shown below. Further, even if additive-free petroleum resin is used, the object of the present invention can be fully achieved. The amount of the petroleum resin added to the polyolefin resin foam or polymer resin sheet is preferably at least 0.5% by weight. Further, the upper limit of the amount to be blended may be within the range that achieves the purpose of the present invention, but is preferably 55% by weight or less. Furthermore, there are no particular limitations on the method of blending the petroleum resin into the polyolefin resin or polymer resin sheet or film, and the means and conditions for foaming the foam, and known methods, means, and conditions may be applied. can. As an example of manufacturing a polyolefin resin foam blended with the petroleum resin of the present invention, first, for example,
At least 0.5% in the above polyolefin resin
Contains petroleum resin, foaming agent, and other additives,
Form a sheet of uniform thickness. After the sheet is crosslinked by a known method, it is heated to a temperature higher than the decomposition temperature of the foaming agent to form a foam. The resulting foam has an apparent density of 0.500 to 0.020 g/cc, a gel fraction of 5 to 70%, preferably 10 to 40%, and a closed cell ratio of 70% or more, preferably 90% or more. It is best to foam it. As the blowing agent, various known thermally decomposable blowing agents such as azodicarbonamide and dinitrosopentamethylenetetramine can be used. Crosslinking methods include a radiation crosslinking method in which ionizing radiation such as X-rays, α, β, and γ rays, ultraviolet rays, etc. are irradiated to impart a crosslinking bond, dibutyl peroxide, 2,5-
Chemical crosslinking methods using chemical crosslinking agents such as dimethyl 2,5-di(t-butylperoxy)hexane and dicumyl peroxide are applied. Furthermore, in order to promote crosslinking, a polyfunctional compound such as divinylbenzene or diallyl phthalate can be used in combination as a crosslinking aid. Further, as other additives, heat stabilizers, ultraviolet absorbers, extenders, nucleating agents, fillers, etc. may be appropriately added. The polymer resin sheet or film of the present invention is not particularly limited, and any of the previously known sheets, films, and low-magnification foams described above may be used. Lamination or composite of a foam and a polymer resin or film is achieved by laminating the foam and foaming on at least one side of the polymer resin sheet or film to be molded when extrusion molding the polymer resin sheet or film. A method in which the foam and polymer resin sheet are individually molded, and then one or both of their adhesive surfaces are heated to thermally bond them, laminated, and integrated into a composite material. It can be laminated and composited by, for example, a method of compositing. [Example] Hereinafter, the foam of the present invention will be explained in more detail with reference to Examples. In the examples, adhesiveness and crushability are values evaluated by the following measuring methods. Adhesion: The adhesion between the foam and the adhered base material was evaluated by the following method. After the composite material adhered to the foam was left at room temperature for 24 hours, the foam was peeled off from the base material, and the adhesion was determined based on the state of the peel. The state where the foam is completely destroyed: ○ The state where the foam is partially damaged: △ The state where no foam remains on the base material side: × Crushability: The foam is heated with a high-frequency welder, Press. The thickness of the pressed foam was measured after being left at room temperature for 48 hours, and the crushability was calculated according to the following formula. (Original foam thickness - Thickness after crushing) / Original foam thickness x 100 Example 1, Comparative Example 1 80% by weight polypropylene copolymer resin containing 4% by weight ethylene and resin density 0.921g 100 parts by weight of a mixture consisting of 20% by weight of polyethylene/cc, 10 parts by weight, 20 parts by weight, 30 parts by weight and 40 parts by weight of petroleum resin with a resin density of 0.999 g/cc, respectively.
A resin composition was prepared by blending parts by weight. Adding azodicarbonamide to these resin compositions
15% and 3% divinylbenzene were mixed uniformly and formed into a sheet with a thickness of 2.0 mm using an extruder. After irradiating these sheets with ionizing radiation of 10.2 Mrad, they are foamed at a temperature of 235°C to produce a foam having a uniform cell structure with an apparent density of 0.032 to 0.036 g/cc and a thickness of 3.8 to 4.3 mm. I got it. ABS resin is extruded into this foam at 170-190℃,
Using that temperature, 25% of the foam thickness was compressed to obtain a laminated composite material. Regarding the adhesion of the obtained composite material, the presence or absence of interfacial peeling was checked at a molding heating temperature of 160°C, and material failure of the foam occurred in that temperature range. On the other hand, Table 1 shows the results of 180° peeling using an autograph at room temperature at a peeling speed of 200 mm/min. On the other hand, as a comparative example, when a foam containing no petroleum resin was evaluated in the same manner as in Example 1, the foam and ABS resin did not adhere at all. These evaluation results are shown in Table 1. In addition, for the crushed foam obtained, high-frequency welder m/c (manufactured by Yamamoto Vinita,
The test was carried out using a VW3500A). In advance, 0.6 mm of polyvinyl chloride resin (PVC) containing ABS resin was set on the foam surface of the composite material in a non-adhesive state, and welding was carried out under the following welding conditions. Oscillation frequency 40.46MHz Anode current 0.6A Mold area 40cm ² Load per area 4.74Kg/cm ² Mold temperature 60℃ Crimping time 6 seconds

[Table] Example 2, Comparative Example 2 Petroleum resin (“Alcon” P-12, manufactured by Arakawa Chemical Co., Ltd.)
A polypropylene resin film (unstretched 40μ) containing 5% by weight of petroleum resin and a polyethylene foam with an apparent density of 0.032 g/cc and a gel fraction of 29% containing 20% by weight of petroleum resin were heated at a constant temperature and speed of hot air. I changed it and laminated it with heat fusion. The adhesion and peeling state of the composite material was evaluated. As Comparative Example 2, a single polypropylene resin film was heat-sealed and laminated under the same conditions as in Example 2. The results are shown in Table 2.

[Effect of idea]

The laminated composite material of the present invention consists of a polyolefin resin foam and a polymer resin sheet or film.
It is directly bonded by heat, and unlike conventional laminated composite materials, there is no adhesive layer at the bonding interface, and the foam layer does not blister, and the insulation properties of the foam layer of laminated composite materials are excellent. , the properties such as cushioning properties, the mechanical strength of the polymer resin sheet or film layer, and decorations such as colors and patterns can be reflected in the laminated composite material without impairing them in any way. Further, when the polyolefin resin foam constituting the laminated composite material contains petroleum resin, high frequency welding is possible due to its high frequency weldability. Furthermore, since it is possible to perform lamination and composite without performing adhesive treatment such as primer processing, it is possible to simplify the process and improve operability, contributing to cost and product quality improvements.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are schematic cross-sectional views showing one embodiment of the laminated composite material of the present invention, respectively. 1... Foam layer, 2... Polymer resin sheet layer or film layer, 3... Skin material layer.

Claims (1)

[Scope of utility model registration request] At least one of the polyolefin resin foam and a sheet or film made of a polymer resin other than the polyolefin resin contains a petroleum resin,
A laminated composite material in which the polyolefin resin foam and a polymer resin sheet or film are integrated by thermal bonding.